ES2727701T3 - Modified diene polymers containing heteroatoms - Google Patents

Abstract

A modified diene polymer, comprising: a substructure in the chain according to formula (X) ** Formula ** and / or a terminal substructure at one end of the chain according to formula (XI), -S-R1 (XI ) in which for formula (X), X is a halogen, preferably a halogen selected from the group of Cl, Br and I, and for formulas (X) and (XI), R1 is selected from a group of - an aromatic amide moiety of the formula (II) C6 (R2) 5- (C = O) -N (R3) -C6 (R2) 4- in which R2 and R3 are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; - a dithiazyl disulfide moiety of the formula (III) ** Formula ** in which R 4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxyl, a linear or branched alkyl moiety having from 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together form the cyclic moiety of the formula (IV); ** Formula ** in which R5 are identical or different and are a hydrogen, hydroxyl moiety, a linear or branched alkyl moiety having from 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 8 atoms of C; - a bistrialkoxysilylalkyl polysulphide moiety of formula (V) (R6O) 3Si- (CH2) n- (Y) m- in which n is an integer from 1 to 12, preferably from 1 to 6; m is an integer from 0 to 4, preferably from 0 to 2; R6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C; Y is sulfur, a group of the formula (VIa), (Vlb), (VIc), (VId) or (VIe) - (Sx-CH2-CH2) n- (VIa) - (Sx-CH2-CH (OH ) -CH2) n- (Vlb) - (Sx-CH2-CH2OCH2-CH2) n- (VIc) - (Sx-CH2- (C6H4) -CH2) n- ** Formula ** in which x is a number integer from 1 to 8, preferably from 2 to 6; p is an integer from 1 to 12, preferably from 1 to 6; R8 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, an alkyl moiety having 1 to 16 C atoms, preferably from 1 to 8 C atoms, or a phenyl moiety, a phenoxy moiety; - a thiuram moiety of the formula (VII) (R9) 2N- (C = Z) - in which Z is sulfur or oxygen, R9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having from 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; - a dithioxantogenate moiety according to formula (VIII) R10-OC (= S) - in which R10 is identical or different and is a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably from 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms, - a phosphonate moiety according to formula (IX) (R11-O) (R11-O) P (Z) - wherein Z is a sulfur or oxygen atom, R11 is identical or different and is a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms.

Description

DESCRIPTION

Modified diene polymers containing heteroatoms

The present invention relates to modified diene polymers containing heteroatoms, to the production of these polymers, to rubber mixtures comprising these modified diene rubbers, and to their use for the production of rubber vulcanizates, which serve, in particular, for the production of highly reinforced rubber molded parts and in the production of tires.

Important desirable properties in tire treads include good adhesion on dry and wet surfaces and high abrasion resistance. It is very difficult to improve the slip resistance of a tire without simultaneously worsening the rolling resistance and abrasion resistance. Low rolling resistance is important for low fuel consumption, and high abrasion resistance is a crucial factor for a long tire life. The wet slip resistance and the rolling resistance of a tire tread depend largely on the dynamic / mechanical properties of the rubbers used in production. To reduce rolling resistance, rubbers with high resilience at high temperatures (60 ° C to 100 ° C) are used for the tread of the tire. On the other hand, in order to reduce the resistance to wet sliding, rubbers are advantageous that have a high damping factor at low temperatures (0 ° C to 23 ° C) or a low resilience in the range of 0 ° C to 23 ° C . To meet this complex profile of requirements, mixtures of various rubbers are used in the tread. Mixtures of one or more rubbers having a relatively high glass transition temperature, such as styrene-butadiene rubber, and one or more rubbers having a relatively low glass transition temperature, such as polybutadiene having a high content of 1 are used. , 4-cis or a styrene-butadiene rubber with a low styrene content and a low vinyl content or a polybutadiene prepared in solution and having a moderate content of 1.4 cis and a low vinyl content.

There are procedures for functionalization in the chain and at a terminal end of the diene polymer chain. A modification method of polydiene terminal groups employs doubly functionalized reagents. These use the polar functional group to react with the polydiene and, using a second polar functional group of the molecule, interact with the filler material, as described by way of example in WO 01/34658 or US- A 6992147. The procedures for introducing functional groups at the beginning of polymer chains by means of functional anionic polymerization initiators are described, for example, in EP 0513217 B1 and EP 0675 140 B1 (initiators with a protected hydroxyl group), the document US 2008/0308204 A1 (initiators containing thioether) and in US 5,792,820 and EP 0 590 490 B1 (alkali metal amides of secondary amines as polymerization initiators). More particularly, EP 0594 107 B1 describes the in situ use of secondary amines as functional polymerization initiators, but does not describe the functionalization of the ends of the polymer chain. In addition, numerous procedures have been developed for the introduction of functional groups at one end of the polymer chains. For example, EP 0180 141 A1 describes the use of 4,4'-bis (dimethylamino) benzophenone or N-methylcaprolactam as functionalization reagents. The use of ethylene oxide and N-vinyl pyrrolidone is known from EP 0 864 606 A1. A number of possible additional functionalization reagents are detailed in U.S. Patent Nos. 4,906,706 and 4,417,029.

EP 2676986 A1 refers to the increase in Mooney viscosity gradually in the production of high molecular weight polybutadiene having more than 95% by weight of cis-1.4 units and less than 1% by weight of units of 1,2-vinyl. This document also refers to a high molecular weight neodymium catalyzed polybutadiene obtained by the process mentioned above; and to mixtures of rubbers comprising a polybutadiene.

EP 2644610 A1 refers to a functionalized elastomer and its use in a tire. The elastomer comprises the reaction product of a living anionic elastomeric polymer and a specific polymerization terminator.

EP 2596963 A1 A refers to a functionalized elastomer comprising the reaction product of a living anionic elastomeric polymer and a specific polymerization terminator. A respective rubber composition and a tire comprising said rubber composition are also disclosed.

WO 2012/092626 A1 describes a process for treating a polymer that has a hydrolysable functionality, the process comprising: (i) providing a polymer that has a hydrolyzable functionality and (ii.) Introducing a specific stabilizing agent to the polymer.

The terminal functionalization reagents used to date have considerable disadvantages, which include complicated production processes and instability due to their reactivity. Functionalization processes in the chain are used less frequently. Functionalizing reagents used for functionalization in the rubber chain include, for example, diazufre dichloride, which leads to a Mooney viscosity jump, as described by way of example in WO 2013/189947 A1. The expression "increase gradual in Mooney viscosity "and similar expressions, for example," subjected to Mooney viscosity jump "or" Mooney viscosity jump ", refers to techniques to significantly improve Mooney viscosity (ML 1 4 at 100 ° C) of Polymers after polymerization and / or the degree of branching The polymer is normally modified with S2Cl2 to branch the polymer by means of a sulfur bridge bond according to the reaction equation it is uematic if:

The degree of branching or Mooney viscosity (ML 1 4 at 100 ° C) is increased accordingly. The reaction scheme shown above describes, by way of example, the "Mooney viscosity jump" for a high cis polybutadiene-styrene copolymer. This reaction can also be performed on any other polymer containing diene.

The modification normally uses sulfur halides, preferably diazufre dichloride, sulfur chloride, sulfur bromide, sulfur dichloride, thionyl chloride, diazufre dibromide or thionyl bromide. To prevent gel formation that may occur during the "Mooney viscosity jump" reaction, an additional step of treating the polymer is carried out, after the polymerization reaction, with a stopping agent, such as, for example, with fatty acids. The "Mooney viscosity jump" is limited to chain modifications with the incorporation of a sulfur atom bridge between polymer chains and a chlorine atom in the polymer chain, which allows only a slight interaction between the rubber and the material of load.

An object of the present invention is to provide a modified diene polymer and a process for producing the same that avoids the disadvantages of those used to date. Surprisingly, the above-mentioned disadvantages of known polymers can now be avoided by using modified diene polymers containing heteroatoms according to the invention and the process for their manufacture.

According to the present invention, a modified polymer is provided comprising a substructure in the chain according to formula (X)

I

a terminal substructure at one end of the chain according to formula (XI),

-S-R1 (XI)

in which

for the formula (X),

X is a halogen, preferably a halogen selected from the group of Cl, Br and I, and for formulas (X) and (XI),

R1 is selected from a group of

- an aromatic amide moiety of the formula (II)

C6 (R2) 5- (C = O) -N (R3) -C6 (R2) 4-

(II)

wherein R2 and R3 are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety that it has 5 to 8 atoms of C;

- a dithiazyl disulfide moiety of the formula (III)

wherein R4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxyl, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear alkoxy moiety or branched having 1 to 12 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together forming the cyclic moiety of the formula (IV) ;

wherein R5 are identical or different and are a hydrogen, hydroxyl moiety, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms;

- a bistrialkoxysilylalkyl polysulphide moiety of formula (V)

(R6O) 3Si- (CH2) n- (Y) m-

(V)

in which

n is an integer from 1 to 12, preferably from 1 to 6;

m is an integer from 0 to 4, preferably from 0 to 2;

R6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C;

Y is sulfur, a group of the formula (VIa), (Vlb), (VIc), (VId) or (VIe)

- (Sx-CH2-CH2) n

(Via)

- (Sx-CH2-CH (OH) -CH2) n- (Vlb)

- (SX-CH2-CH2OCH2-CH2V

(VIc)

- (Sx-CH2- (CeH4) -CH2) n- (Vld)

in which

x is an integer from 1 to 8, preferably from 2 to 6;

p is an integer from 1 to 12, preferably from 1 to 6;

R are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, an alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 atoms of C, or a phenyl moiety, a phenoxy moiety;

- a thiuram residue of the formula (VII)

(R9) 2N- (C = Z) -

(VII)

in which

Z is sulfur or oxygen,

R9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms;

- a dithioxantogenate moiety according to formula (VIII)

R10-O-C (= S) -

(VIII)

in which

R10 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C,

- a phosphonate residue according to formula (IX)

(R11-O) (R11-O) P (Z) -

(IX)

in which

Z is a sulfur or oxygen atom,

R11 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 5 8 atoms of C.

In addition, the modified polymer can also comprise a sulfur bridge between polymer chains according to formula (XII)

And when the modified polymer is a diene polymer or a diene copolymer obtained by copolymerizing at least one conjugated diene monomer or at least one diene monomer conjugated to at least one vinyl aromatic comonomer, for example, the polymer is preferably a polybutadiene or a butadiene-styrene copolymer.

In another embodiment of the present invention, there is provided a process for producing a modified polymer, as well as the modified polymer obtained according to the process, which comprises the steps of reacting a diene polymer with a halogenated sulfur organic compound, forming the halogenated sulfur organic compound by reacting a halogen with a sulfur compound with the general formula (Ia) and / or (Ib) and / or (Ic):

R1-S-S-R1

(I-a),

R1-S- (S) n-S-R1, in which 1 <n <8

(I-b),

R1-SH

(I-c),

in which R1 are identical or different and are selected from a group of

- an aromatic amide moiety of the formula (II)

C6 (R2) 5- (C = O) -N (R3) -C6 (R2) 4-

(II)

wherein R2 and R3 are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety that it has 5 to 8 atoms of C;

- dithiazyl disulfides of the formula (III)

wherein R4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxyl, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear alkoxy moiety or branched having 1 to 12 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together forming the cyclic moiety of the formula (IV) ;

wherein R5 are identical or different and are a hydrogen, hydroxyl moiety, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms;

- a bistrialkoxysilylalkyl polysulphide moiety of formula (V)

(R6O) 3Si- (CH2) n- (Y) m-

(V)

in which

n is an integer from 1 to 12, preferably from 1 to 6;

m is an integer from 0 to 4, preferably from 0 to 2;

R6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C;

Y is sulfur, a group of the formula (VIa), (Vlb), (VIc), (VId) or (VIe)

- (Sx-CH2-CH2) n- (VIa)

- (Sx-CH2-CH (OH) -CH2) n- (Vlb)

- (Sx-CH2-CH2OCH2-CH2) n- (VIc)

- (Sx-CH2- (C6H4) -CH2) n- (Vld)

in which

x is an integer from 1 to 8, preferably from 2 to 6;

p is an integer from 1 to 12, preferably from 1 to 6;

R8 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, an alkyl moiety having 1 to 16 C atoms, preferably from 1 to 8 C atoms, or a phenyl moiety, a phenoxy moiety;

- a thiuram residue of the formula (VII)

(R9) 2N- (C = Z) -

(VII)

in which

Z is sulfur or oxygen,

R9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C;

- a dithioxantogenate moiety according to formula (VIII)

R10-O-C (= S) -

(VIII)

in which

R10 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C,

- a phosphonate residue according to formula (IX)

(R11-O) (R11-O) P (Z) -

(IX)

in which

Z is a sulfur or oxygen atom,

R11 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 5 8 atoms of C.

The process may comprise, in another embodiment, reacting the diene polymer with a Mooney viscosity jump functionalization reagent, for example, when said reagent is a sulfur halide, preferably diazufre dichloride, sulfur chloride, bromide of sulfur, sulfur dichloride, thionyl chloride, diazufre dibromide or thionyl bromide. In order to avoid gel formation that can occur during the "Mooney viscosity jump" reaction, an additional step of treating the polymer is performed, after the polymerization reaction, with one or more fatty acids.

In another embodiment of the invention, a rubber mixture is provided comprising a modified rubber as provided above and one or more of a rubber auxiliary and / or at least one additional rubber other than the modified polymer rubber. Rubber auxiliaries generally improve the processing properties of rubber compositions, or serve to cross-link rubber compositions, or improve the physical properties of vulcanizates produced from the rubber compositions of the invention for specific use. planned of the vulcanized ones, or improve the interaction between the rubber and the load material or serve to couple the rubber to the load material. Examples of rubber auxiliaries are crosslinking agents, for example, sulfur compounds or sulfur donor compounds, and also reaction accelerators, antioxidants, thermal stabilizers, light stabilizers, anti-ozone agents, processing aids, plasticizers, agents of adhesion, expanding agents, dyes, pigments, waxes, diluents, organic acids, silanes, retardants, metal oxides, diluting oils, for example, oil DAE (distilled aromatic extract), TDAE oil (treated distilled aromatic extract), MES oil (mild extraction solvent), RAE oil (residual aromatic extract), TRAE oil (treated residual aromatic extract), heavy naphthenic and naphthenic oils, and also activators

In another embodiment, a rubber mixture comprising the above modified polymer and 10 to 500 parts by weight of filler material, relative to 100 parts by weight of the modified polymer is provided. The diene polymer of the modified polymer of the invention is prepared by polymerization reaction, preferably, either anionic solution polymerization or polymerization by means of coordination catalysts.

The conjugated diene monomers that can be used are any known diene that is conventionally used for production. Examples that may be mentioned are: 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, isoprene, piperylene, 1,3-hexadiene, 1,3-octadiene , 2-phenyl-1,3-butadiene, preferably 1,3-butadiene and isoprene, and also mixtures thereof. In one embodiment, 1,3-butadiene is used.

Examples of vinyl aromatic monomers that can be used are styrene, o-, m- and / or p-methylstyrene, p-tert-butyl styrene, a-methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene and / or divinylnaphthalene. In one embodiment styrene is used.

In another embodiment of the invention, the diene polymer is a styrene-butadiene copolymer.

In another embodiment of the invention, the content of vinyl aromatic monomers copolymerized in the modified diene polymer is 0 to 60% by weight, preferably 15 to 45% by weight, and its content of dienes is 40 to 100% by weight, preferably 55 to 85% by weight, the content of dienes having 1,2 bond (vinyl content) in the diets of 0.5 to 95% by weight, preferably 10 to 85% by weight, and The totality composed of vinyl aromatic monomers and copolymerized dienes gives a total of 100%.

The initiators for the anionic solution polymerization reactions are those based on alkali metals or alkaline earth metals, with n-butyllithium being an example. It is also possible to use randomizers and known control agents for the microstructure of the polymer, examples being the same potassium tert-amylalcholate, sodium tert-amylalcholate and tert-butoxy-ethoxyethane. Solution polymerization reactions of this type are known and are described by way of example by I. Franta, Elastomers and Rubber Compounding Materials, Elsevier 1989, pages 113-131, and in Comprehensive Polymer Science, Vol. 4, Part II ( Pergamon Press Ltd., Oxford 1989), pages 53-108.

The catalysts used for the polymerization by means of coordination catalysts are preferably rare earth metal compounds, such as those described, for example, in EP-B-011184 or EP-A 1245600. It is also possible use any of the known Ziegler-Natta catalysts for the polymerization reaction, for example those based on titanium, cobalt, vanadium or nickel compounds, or also based on rare earth metal compounds. The Ziegler-Natta catalysts mentioned can be used individually or in a mixture with each other.

It is preferable to use Ziegler-Natta catalysts based on rare earth metal compounds, for example cerium, lanthanum, praseodymium, gadolinium or neodymium compounds, when these are soluble in hydrocarbons. It is preferable to use, in particular, as Ziegler-Natta catalysts, the corresponding salts of rare earth metals, for example, neodymium carboxylates, in particular neodymium neodecanoate, neodymium octanoate, neodymium naphthenate, 2,2-diethylhexanoate neodymium or neodymium 2,2-diethylheptanoate, or the corresponding salts of lanthanum or praseodymium. In addition, the Ziegler-Natta catalysts that can be used also comprise metallocene-based catalyst systems, for example those described in EP-A 1025136 and EP-A 1078939.

The polymerization reaction can take place by conventional processes in one or more stages and, respectively, in batches or in continuous. Preference is given to the continuous process in a cascade of reactors composed of a plurality of reactors connected in series, preferably at least 2, in particular 2 to 5.

The polymerization reaction can be carried out in a solvent. Preference is given to inert aprotic solvents, for example, paraffinic hydrocarbons, such as isomeric pentanes, hexanes, heptanes, octanes, decans, 2,4-trimethylpentane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, or aromatic hydrocarbons, such as benzene, toluene, , ethylbenzene, xylene, diethylbenzene or propylbenzene. These solvents can be used individually or in combination. Preference is given to cyclohexane and n-hexane. It is also possible to mix them with polar solvents. The polymerization reaction is preferably carried out in the presence of the inert aprotic solvents mentioned above, optionally mixed with polar solvents. The amount of solvent for the process of the invention is generally of 1000 to 100 g, preferably 500 to 150 g, with respect to 100 g of the total amount of monomer used. It is also possible, of course, that the monomers used are polymerized in the absence of solvents.

The polymerization temperature can vary widely and is generally in the range of 0 ° C to 200 ° C, preferably 40 ° C to 130 ° C. The reaction time also varies widely from several minutes to several hours. The polymerization reaction is generally carried out within a period of about 30 minutes to 8 hours, preferably 1 to 4 hours. It can be carried out at atmospheric pressure or at elevated pressure (from 1 to 10 bar).

The polymerization of the unsaturated monomers can preferably be carried out until complete conversion of the monomers used. It is also possible to interrupt the polymerization reaction prematurely as required by the desired properties of the modified polymer, for example at approximately 80% conversion of the monomers. After the polymerization reaction, the unconverted diene can be removed, if desired, by distillation under reduced pressure, for example in an ultrafast stage.

At another stage of the process, the halogenated sulfur organic compounds or, respectively, a mixture of said compounds, for use in the modification reaction are formed from a halogenation reaction of a sulfur compound (also referred to herein as compounds organic sulphides) with the general formula (la) and / or (Ib) and / or (Ic):

R1-S-S-R1

(the),

R1-S- (S) n-S-R1, in which 1 <n <8

(l-b),

R1-SH

(l-c),

in which R1 are identical or different and are selected from a group of

- an aromatic amide moiety of the formula (ll)

C6 (R2) 5- (C = O) -N (R3) -C6 (R2) 4-

(II)

wherein R ² and ³ R are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a moiety cycloalkyl having 5 to 8 C atoms;

- a dithiazyl disulfide moiety of the formula (III)

wherein R4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxyl, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear alkoxy moiety or branched having 1 to 12 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together forming the cyclic moiety of the formula (IV) ;

wherein R5 are identical or different and are a hydrogen, hydroxyl moiety, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms;

- a bistrialkoxysilylalkyl polysulphide moiety of formula (V)

(R6O) 3Si- (CH2) n- (Y) m-

(V)

in which

n is an integer from 1 to 12, preferably from 1 to 6;

m is an integer from 0 to 4, preferably from 0 to 2;

R6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C;

Y is sulfur, a group of the formula (VIa), (Vlb), (VIc), (VId) or (VIe)

- (Sx-CH2-CH2) n- (VIa)

- (Sx-CH2-CH (OH) -CH2) n- (Vlb)

- (Sx-CH2-CH2OCH2-CH2) n- (VIc)

- (Sx-CH2- (C6H4) -CH2) n- (Vld)

in which

x is an integer from 1 to 8, preferably from 2 to 6;

p is an integer from 1 to 12, preferably from 1 to 6;

R are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, an alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a phenoxy moiety;

- a thiuram residue of the formula (VII)

(R9) 2N- (C = Z) -

(VII)

in which

Z is sulfur or oxygen,

R9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety,

or a cycloalkyl moiety having 5 to 8 C atoms;

- a dithioxantogenate moiety according to formula (VIII)

R10-O-C (= S) -

(VIII)

in which

R10 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C,

- a phosphonate residue according to formula (IX)

(R11-O) (R11-O) P (Z) -

(IX)

in which

Z is a sulfur or oxygen atom,

R11 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 5 8 atoms of C.

Among the group of the sulphurated organic compounds to be halogenated are, for example, disulfide compounds such as di (benzothiazol-2-yl) disulfide (Vulkacit® DM / C) or tetrabenzyluram disulfide compounds ( Perkacit® TBzTD) or polysulfide compounds such as di (2-ethylhexyl) di (thiophosphonate) polysulphide (Rhenocure® SDT / S).

The halogenation reaction of the sulphurated organic compounds can be carried out using various known halogens, including, but not limited to, chlorine, bromine, iodine or other chlorinating agents known to those skilled in the art, such as carbon tetrachloride, N- chlorosuccimide, cyanuric chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, sulfuryl chloride, thionyl chloride, sulfur chlorides such as S2Cl2.

The halogenation reaction can be carried out with 0.05 to 10 equivalents of halogen, preferably with 0.5 to 5 equivalents of halogen, preferably with 0.7 to 2.1 equivalents of halogen, with respect to the sulfurized organic compounds. The reaction solvent may be any non-protic solvent, such as n-hexane, isohexanes, cyclohexanes or mixtures thereof, any other alkanes, aromatic compounds such as benzene, toluene or xylenes, ethers such as diethyl ether or methyl t-butyl ether . The solvents mentioned are examples and are not limiting. In one embodiment, the halogenation reaction solvent is chosen to be the same as that of the polymerization reaction.

The halogenation reaction can be carried out at temperatures between 0 ° C and 100 ° C, but is not limited to these temperatures. In one embodiment, the temperature is chosen to be approximately the same as that of the polymerization reaction.

In another step, the modification reaction according to the invention is carried out when the halogenated sulfur organic compounds and the polymerization mixture obtained during the polymerization reaction are mixed and reacted with each other.

A modified polymer is formed by the modification reaction having a substructure in the chain according to formula (X)

(X),

I

a terminal substructure at one end of the chain according to formula (XI),

-S-R1 (XI)

in which

for formula (X), X is a halogen, preferably a halogen selected from the group of Cl, Br and I, and for formulas (X) and (XI),

R1 is as defined above.

The amount of halogenated sulfur organic compounds used depends on the desired degree of modification of the polymeric material. It is preferred that the ratio of sulfur organic compounds with respect to the polymer is in the range of 0.05 to 10 phr, in particular 0.25 to 5 phr, 1 phr corresponding to one gram of substance with respect to 100 grams of polymer.

In the modification reaction it is advantageous that no harmful compounds are present that may adversely affect the modification reaction. Examples of harmful compounds of this type are carbon dioxide, oxygen, water, alcohols and organic and inorganic acids.

The modification reaction can be carried out at temperatures corresponding approximately to the temperatures of the polymerization reaction. This means that the modification reaction is carried out at temperatures of about 0 ° C to 200 ° C, preferably from 40 ° C to 130 ° C. The modification reaction can also be carried out at atmospheric pressure or at elevated pressure (from 1 to 10 bar).

The time of the modification reaction can vary widely. In one embodiment, the time is in the range of about 1 minute to about 1 hour.

The modified polymers resulting from the modification reaction, in one embodiment, are obtained by treating the reaction mixture with terminating reagents comprising active hydrogen, for example, alcohols or water or appropriate mixtures. It is advantageous to add antioxidants to the reaction mixture before isolating the modified polymer. The modified polymer is conventionally isolated, for example, by steam distillation or flocculation with a suitable flocculating agent, for example alcohols. The flocculated polymer is then removed, by way of example, from the resulting medium by centrifugation or extrusion. The residual solvent and other volatile constituents can be removed from the insulated polymer by heating, optionally under reduced pressure or in a stream of air produced by a blower.

The molecular weight of the modified polymers according to the invention can vary widely. In one embodiment, the number average molecular weight of the modified polymer is in the range of about 1000 to about 2,000,000. The content of 1,2 bonds (vinyl content) is preferably 0.3 to 1% by weight.

The modification reaction may further comprise subjecting the polymer to a jump of Mooney viscosity. The Mooney viscosity jump can use, as a Mooney viscosity jump reagent, sulfur halides, preferably diazufre dichloride, sulfur chloride, sulfur bromide, sulfur dichloride, thionyl chloride, diazufre dichromide or thionyl bromide. To avoid gel formation during the Mooney viscosity jump reaction, an additional stage of polymer treatment is performed, after the polymerization reaction, with one or more fatty acids. In one embodiment, the modified polymer is subjected to a Mooney viscosity jump by reaction with S2Cl2, whereby the Mooney viscosity of the modified polymer increases with with respect to the polymer without said addition. A modified polymer subjected to a Mooney viscosity jump having a sulfur bridge substructure between polymer chains, according to formula (XII) is obtained by means of a Mooney viscosity jump.

and which also comprises a substructure in the chain according to formula (X)

I

a terminal substructure at a chain end according to formula (XI),

-S-R1 (XI)

in which

for formulas (XII) and (X),

X is a halogen, preferably, a halogen selected from the group of Cl, Br and I, and

for formulas (X) and (XI),

R1 is as defined above.

As will be appreciated, it is possible in another embodiment of the invention to carry out the modification reaction (i.e., the reaction between the polymers and the halogenated sulfur organic compounds) directly after polymerization without the need for isolation or other processing of the reactants, as well as, optionally, perform a Mooney viscosity jump directly without the need for insulation or other processing of the modified polymers. Therefore, the present invention further provides a process for the production of the modified polymers of the invention in which the conjugated diene monomers are polymerized in the presence of inert organic aprotic solvents (polymer solution), and the polymers resulting from the Polymerization reaction is reacted with halogenated sulfur organic compounds that are added directly to the polymer solution. And, in another embodiment, the modified polymers resulting from the modification reaction are reacted by Mooney viscosity jump with functionalization reagents, for example, diazufre dichloride, which are also added directly to the polymer solution.

The amount of halogenated sulfur compounds to be used can vary widely. In one embodiment, approximately 0.05 phr to 10 phr by weight per 100 parts by weight of all monomers used for the polymerization reaction are used.

The amount of Mooney viscosity jump functionalization reagent to be used can vary widely. In one embodiment, about 0.01 phr to 2 phr, preferably 0.04 to 1 phr, by weight per 100 parts by weight of all monomers used for the polymerization reaction are used. The modified polymers of the invention can be used for the production of rubber mixtures, in turn for the production of vulcanizates, especially for the production of tires, especially tire treads, which have a particularly low rolling resistance together. with a high resistance to wet sliding and high resistance to abrasion, or layers thereof, or molded parts of rubber. Said rubber mixtures preferably comprise rubber auxiliaries (the examples are components for the formation of composite materials, fillers, dyes, pigments, softeners, rubber chemicals, processing aids, diluting oils and reinforcing agents) and / or one or more additional rubbers. Vulcanizable compositions comprising said mixtures of Rubber preferably also comprises at least one cross-linking system, comprising at least one cross-linking agent and, optionally, one or more cross-linking accelerators, or vulcanizing reagents.

Vulcanizable rubber compositions can be produced in a one-stage or multi-stage process, with preference given to 2 to 3 mixing stages. For example, sulfur and the accelerator can be added in a separate mixing stage, for example in a roller, the preferred temperatures being in the range of 30 to 90 ° C. In one embodiment, a process for producing vulcanizates is provided which comprises vulcanizing the vulcanizable composition, preferably in the course of a forming process, preferably at a temperature in the range of 100 ° C to 200 ° C, more preferably from 120 ° C to 190 ° C and especially preferably from 130 ° C to 180 ° C.

Preference is given to the addition of sulfur and accelerator in the last mixing stage. Examples of suitable equipment for the production of vulcanizable rubber compositions include rollers, kneaders, internal mixtures or mixing extruders. Therefore, the invention further provides vulcanizable rubber compositions comprising the modified polymers.

The vulcanizable rubber compositions of the invention are also suitable for the production of molded parts, for example, for the production of cable sleeves, hoses, transmission belts, conveyor belts, roller covers, shoe soles, gasket rings and damping elements. Additional rubbers are, for example, natural rubber and synthetic rubbers. If present, the amount thereof is preferably within the range of 0.5 to 95%, preferably 10 to 80% by weight, with respect to the total amount of polymer present in the mixture. The amount of additionally added rubbers is again governed by the respective end use of the mixtures of the invention.

As an example, synthetic rubbers known in the literature are listed. These include, among others, BR polybutadiene

ABR C1-C4 alkyl butadiene / acrylate copolymers

IR polyisoprene

E-SBR styrene-butadiene copolymers having a styrene content of 1-60%, preferably 20-50% by weight, prepared by emulsion polymerization

S-SBR styrene-butadiene copolymers having a styrene content of 1-60%, preferably 15-45% by weight, prepared by solution polymerization

IIR isobutylene-isoprene copolymers

NBR butadiene-acrylonitrile copolymers having an acrylonitrile content of 5 to 60%, preferably 10 to 40% by weight

HNBR NBR rubber partially hydrogenated or fully hydrogenated

EPDM ethylene-propylene-diene terpolymers

and mixtures of the rubbers mentioned above. For the production of automobile tires, natural rubber, E-SBR and S-SBR with a glass transition temperature exceeding -60 ° C, polybutadiene rubber having a high cis content (> 90%) are of particular interest. and it has been prepared with catalysts based on Ni, Co, Ti or Nd, and polybutadiene rubber having a vinyl content of up to 80% and mixtures thereof.

Useful fillers for vulcanizable rubber compositions include all known fillers that are used in the rubber industry. These include active and inactive loading materials. The following can be mentioned by way of example:

finely divided silicas, produced, for example, by precipitation of silicate solutions or flame hydrolysis of silicon halides having specific surface areas of 5-1000, preferably 20-400, m2 / g (BET surface area) and having primary particle sizes of 10-400 nm. Silicas may also optionally be present as mixed oxides with other metal oxides, such as oxides of Al, Mg, Ca, Ba, Zn, Zr, Ti;

synthetic silicates, such as aluminum silicate, alkaline earth metal silicates such as magnesium silicate or calcium silicate, which have BET surface areas of 20-400 m2 / g and primary particle diameters 10-400 nm;

natural silicates, such as kaolin and other natural silicas;

glass fibers and fiberglass products (mats, strands) or glass microspheres;

metal oxides, such as zinc oxide, calcium oxide, magnesium oxide, aluminum oxide; metal carbonates, such as magnesium carbonate, calcium carbonate, zinc carbonate; metal hydroxides, for example aluminum hydroxide, magnesium hydroxide;

metal sulfates, such as calcium sulfate, barium sulfate;

Carbon blacks: The carbon blacks to be used herein are carbon blacks produced by the process of lamp black, channel black, furnace black, gas black, thermal black, acetylene black or light arc and have BET surface areas of 9 to 200 m2 / g, for example, carbon blacks SAF, ISAF-LS, ISAF-HM, ISAF-LM, ISAF-HS, CF, SCF, HAF-LS, HAF, HAF-HS , FF-HS, SPF, XCF, FEF-LS, FEF, FEF-HS, GPF-HS, GPF, APF, SRF-LS, SRF-LM, SRF-HS, SRF-HM and MT, or ASTM carbon blacks N110, N219, N220, N231, N234, N242, N294, N326, N327, N330, N332, N339, N347, N351, N356, N358, N375, N472, N539, N550, N568, N650, N660, N754, N760 N765, N774, N787 and N990; I

rubber gels, especially those based on BR, E-SBR and / or polychloroprene having particle sizes of 5 to 1000 nm.

The fillers used are preferably finely divided and / or carbon black silicas.

The aforementioned fillers can be used alone or as a mixture. In a preferred embodiment, the vulcanizable rubber compositions comprise, as fillers, a mixture of light colored fillers, such as finely divided silicas, and carbon blacks, the mixing ratio of fillers being light colors with respect to carbon blacks of 0.01: 1 to 50: 1, preferably 0.05: 1 to 20: 1.

Loading materials are used herein in amounts in the range of 10 to 500 parts by weight based on 100 parts by weight of rubber. Preference is given to the use of 20 to 200 parts by weight.

The invention also provides the use of modified polymers of the invention for the production of tires and tire components, golf balls and rubber technical articles, and also rubber reinforced plastics, for example ABS plastics and HIPS plastics. If the modified polymers of the invention are used in vulcanizable rubber compositions for the production of tires, it is possible, among other things, to discern a marked decrease in such delta loss factors in dynamic damping and amplitude scanning, and also an increase in the rebound effect at 23 ° C and 60 ° C, and also an increase in hardness and modules in the tensile test.

Although the preferred embodiment of the present invention has been described herein with reference to the accompanying drawings, it should be understood that the invention is not limited to that precise embodiment, and that various other changes and modifications can be made to the same by a person skilled in the art without departing from the scope or spirit of the invention. The following examples serve to illustrate the invention without any associated limiting effect.

Examples

I. Polymers

Example of the invention 1

Preparation of Fx-PBR1

Preparation of modification reagent No. 1: Perkacit® TBzTD (109 g) was dispersed in dry hexane (330 g) at 50 ° C. Chlorine gas (17 g) is introduced. The reaction mixture was stirred for 30 min at 50 ° C. This provided a transparent yellow solution. The amount necessary for functionalization was charged directly from this solution to a polymerization reactor with the following living polymer cement.

71.4 kg of a living polymer solution ("cement") at 18.2% are loaded under inert conditions of dry nitrogen in a 160 l steel reactor, which is equipped with a stirrer, temperature control and a burette . To control the Mooney viscosity of the cement, approximately 300 g of the cement was transferred in the atmosphere of Nitrogen to a 1 l bottle, briefly stopped with 100 g of ethanol, stabilized with 0.2 g of Irganox® 1520 and dried at 100 ° C in a hot mill to obtain a solid sample. The resulting Mooney viscosity of the cement (ML 1 4 at 100 ° C) was found to be 42.4 MU.

243 g of modification reagent No. 1 were placed in the burette and added with mixing at 58 ° C to the reactor. The reaction mixture is stirred for 30 min. The mixture is then stabilized with 0.2 phr of Irganox® 1520. The polymer solution is subjected to drag distillation (pH 8-9) and the rubber is dried under vacuum at 65 ° C for 48 hours to a level of residual humidity <0.5% and it was observed that it presents the following analytical data: Mooney viscosity (ML 1 4 at 100 ° C): 52.5 MU, Mooney tension relaxation MSR 0.58; 200 mPas viscosity solution; and microstructure by FT-IR: 1,4-cis-BR: 97.7%, 1,4-trans-BR: 1.8%, 1,2-vinyl-BR: 0.5%.

Example of the invention 2

Preparation of Fx-PBR2

Preparation of modification reagent No. 2: Vulkacit® DM (50 g) was dispersed in cyclohexane (400 g) at 50 ° C. Chlorine gas (12.8 g) was introduced and the reaction mixture was stirred for 30 minutes at 50 ° C. This provided a transparent solution. The amount necessary for functionalization was charged directly from this solution to a polymerization reactor with the following living polymer cement.

68.1 kg of 18.2% living polymer solution cement was loaded into a reactor in a manner analogous to Example 1. The Mooney viscosity of the cement (ML 1 4 at 100 ° C) was 46.4 MU. 462 g of modification reagent No. 2 was added at 63 ° C, and the reaction mixture was stirred for 30 min. The mixture was then stabilized with 0.2 phr of Irganox® 1520. The polymer solution was subjected to drag distillation (pH 8-9) and the rubber was dried under vacuum at 65 ° C for 48 hours to a humidity level. residual <0.5% and it was observed that it presented the following analytical data:

Mooney viscosity (ML 1 4 at 100 ° C): 43.5 MU, Mooney tension relaxation MSR 0.75; solution viscosity 184 mPas; FT-IR microstructure: 1,4-cis-BR: 97.7%, 1,4-trans-BR: 1.8%, 1,2-vinyl-BR: 0.5%.

Reference Example 3

71.4 kg of an 18.2% living polymer solution cement is loaded into a reactor analogously to example 1 and stopped briefly by adding 300 g of isopropanol. The reactor was stirred for 1 hour. The Mooney viscosity of the cement (ML 1 4 at 100 ° C) was 33.0 MU. 3.9 g of lauric acid dissolved in 100 g of hexane were added and the reactor was stirred for 30 minutes. 26 g of S2Cl2 was added at 60 ° C, and the reaction mixture was stirred again for 30 minutes. The mixture was then stabilized with the addition of 0.2 phr of Irganox® 1520. The polymer solution was subjected to drag distillation (pH 8-9) and the rubber was dried under vacuum at 65 ° C for 48 hours until a residual humidity level <0.5% and it was observed that it presents the following analytical data:

Mooney viscosity (ML 1 4 at 100 ° C): 43.2 MU, Mooney tension relaxation MSR 0.55; solution viscosity 157 mPas.

Example of the invention 4

Preparation of Fx-PBR2 subjected to Mooney viscosity jump

1 kg of the functionalized NdBR of Example 2 (Fx-PBR2) was dissolved in 9 kg of hexane in an inert atmosphere. 0.20 phr of lauric acid was added and the reaction mixture was heated to 65 ° C. 3 g of S2Cl2 was added slowly and the reaction mixture was stirred for 30 minutes. The reaction was cooled to room temperature and a mixture of 0.5 phr of epoxidized soybean oil (ESBO) and 0.5 phr of Vulkanox® 4020 was added. The procedure was repeated a second time and both solutions were terminated together. The product was precipitated in 60 l of ethanol and dried under vacuum at 65 ° C for 48 hours at a residual humidity level <0.5% and it was observed that it had the following analytical data:

Mooney viscosity (ML 1 4 at 100 ° C): 65.7 MU, Mooney tension relaxation MSR 0.42.

II: Vulcanization tests

The following properties were determined in the vulcanized products according to the established norms:

- DIN 53505: Shore A hardness at 60 ° C

- DIN 53512: rebound resilience at 60 ° C

- DIN 53504: tensile test with 100% and 300% voltage values (S100 and S300)

- DIN53513: dynamic damping by means of the Eplexor equipment: the Eplexor equipment (Eplexor 500 N) from Gabo-Testanlagen GmbH, Ahlden, Germany, was used to determine the dynamic properties (temperature dependence of the storage module E 'in the interval from temperature of -60 ° C to 0 ° C and also so 5 to 60 ° C). The values were determined according to DIN53513 at 10 Hz in strips of Ares in the temperature range of -100 ° C to 100 ° C at a heating rate of 1 K / min.

The procedure was used to obtain the following variables, the terminology of this document being in accordance with ASTM 5992-96:

tan 5 (60 ° C): loss factor (E "/ E ') at 60 ° C.

tan 5 (60 ° C) is a measure of the loss of hysteresis of the tire under operating conditions. As it decreases so 5 (60 ° C), the rolling resistance of the tire decreases.

- DIN53513-1990: elastic properties: an MTS elastomer test system (MTS Flex Test) from MTS was used to determine the elastic properties. The measurements were made according to DIN53513-1990 in cylindrical samples (2 samples each of 20 x 6 mm) with a total compression of 2 mm at a temperature of 60 ° C and a measurement frequency of 1 Hz in the range of amplitude scan from 0.1 to 40%.

The procedure was used to obtain the following variables, the terminology of this document being in accordance with ASTM 5992-96:

G * (15%): dynamic module at 15% amplitude scan

tan 5 (max): maximum loss factor (G "/ G ') of the entire measuring range at 60 ° C.

tan 5 (max) is a measure of the loss of hysteresis of the tire under operating conditions. As it decreases so 5 (max), the rolling resistance of the tire decreases.

Comparison of Mooney parameters in polymers of several modified NdBR according to the invention and standard NdBR

The following substances were used in the compounds:

All amounts mentioned below are provided in phr (parts per hundred) of rubber. The following substances were used for mixing studies on modified NdBR (Fx-PBR1 and 2), on reference example 3 and on the standard Bd® CB 24 NdBR with carbon black:

The following are comparative results for the composite and vulcanized materials of the BR / carbon black mixtures.

The following substances were used for mixing studies of modified NdBR (Fx-PBR2 and example 4) and in standard NdBR Buna® CB 24 with natural rubber and carbon black:

The following are comparative results for the composite and vulcanized materials of the BR / carbon black mixtures.

In the two studies of the above compounds, the modified polymers of Examples 1 and 2 of the invention and the Mooney viscosity modified and skipped polymer of Example 4 of the invention show a better tendency to rolling resistance with respect to reference rubber, which is indicated by greater rebound resilience at 60 ° C, a lower tan 5 (max) in the 60 ° C amplitude scan and for examples 2 and 4 also a tan 5 (60 ° C ) lower in dynamic damping in the Eplexor. In addition, the examples of the invention 1, 2 and 4 have a higher S300 module in the tensile test at room temperature and a higher dynamic G * module at a 15% amplitude sweep, indicating a network formation stronger due to the increased interactions between the polymer and the filler material.

Claims (17)

1. A modified diene polymer, comprising: a substructure in the chain according to formula (X)

I a terminal substructure at one end of the chain according to formula (XI), -S-R1 (XI) in which for the formula (X), X is a halogen, preferably a halogen selected from the group of Cl, Br and I, and for formulas (X) and (XI), R1 is selected from a group of - an aromatic amide moiety of the formula (II) C6 (R2) 5- (C = O) -N (R3) -C6 (R2) 4- (II) wherein R ² and ³ R are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a moiety cycloalkyl having 5 to 8 C atoms; - a dithiazyl disulfide moiety of the formula (III)

wherein R4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxyl, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear alkoxy moiety or branched having 1 to 12 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together forming the cyclic moiety of the formula (IV) ;

wherein R5 are identical or different and are a hydrogen, hydroxyl moiety, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 8 atoms of C; - a bistrialkoxysilylalkyl polysulphide moiety of formula (V) (R6O) 3Si- (CH2) n- (Y) m- (V) in which n is an integer from 1 to 12, preferably from 1 to 6; m is an integer from 0 to 4, preferably from 0 to 2; R6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C; Y is sulfur, a group of the formula (VIa), (Vlb), (VIc), (VId) or (VIe) - (Sx-CH2-CH2) n- (VIa) - (Sx-CH2-CH (OH) -CH2) n- (Vlb) - (Sx-CH2-CH2OCH2-CH2) n- (VIc) - (Sx-CH2- (C6H4) -CH2) n- (Vld)

in which x is an integer from 1 to 8, preferably from 2 to 6; p is an integer from 1 to 12, preferably from 1 to 6; R are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, an alkyl moiety having 1 to 16 C atoms, preferably from 1 to 8 C atoms, or a phenyl moiety, a phenoxy moiety; - a thiuram residue of the formula (VII) (R9) 2N- (C = Z) - (VII) in which Z is sulfur or oxygen, R9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; - a dithioxantogenate moiety according to formula (VIII) R10-O-C (= S) - (VIII) in which R10 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C, - a phosphonate residue according to formula (IX) (R11-O) (R11-O) P (Z) - (IX) in which Z is a sulfur or oxygen atom, R11 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 5 8 atoms of C. 2. The modified polymer according to claim 1, further comprising: a sulfur bridge between polymer chains according to formula (XII)

3. The modified polymer according to claim 1 or 2, the polymer being a diene homopolymer or a diene copolymer obtained by the copolymerization of conjugated diene monomers or conjugated diene monomers with vinyl aromatic comonomers. 4. The modified polymer according to claim 1 or 2, wherein the polymer is a polybutadiene or polybutadiene-styrene copolymer. 5. A process to produce a modified polymer, comprising the steps of: reacting a diene polymer with at least one halogenated sulfur organic compound, wherein the halogenated sulfur organic compound is formed by reacting a halogen with a sulfur compound with the general formula (Ia) and / or (Ib) and / or Ic): R1-S-S-R1 (I-a), R1-S- (S) n-S-R1, in which 1 <n <8 (I-b), R1-SH (I-c), in which R1 are identical or different and are selected from a group of - an aromatic amide moiety of the formula (II) C6 (R2) 5- (C = O) -N (R3) -C6 (R2) 4- (II) wherein R2 and R3 are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety that it has 5 to 8 atoms of C; - a dithiazyl disulfide moiety of the formula (III)

wherein R4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxyl, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear alkoxy moiety or branched having 1 to 12 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together forming the cyclic moiety of the formula (IV) ;

wherein R5 are identical or different and are a hydrogen, hydroxyl moiety, a linear or branched alkyl moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms; - a bistrialkoxysilylalkyl polysulphide moiety of formula (V) (R6O) 3Si- (CH2) n- (Y) m- (V) in which n is an integer from 1 to 12, preferably from 1 to 6; m is an integer from 0 to 4, preferably from 0 to 2; R6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C; Y is sulfur, a group of the formula (VIa), (Vlb), (VIc), (VId) or (VIe) - (Sx-CH2-CH2) n (Via) - (Sx-CH2-CH (OH) -CH2) n- (Vlb) - (SX-CH2-CH2OCH2-CH2V (VIc) - (Sx-CH2- (CeH4) -CH2) n-

in which x is an integer from 1 to 8, preferably from 2 to 6; p is an integer from 1 to 12, preferably from 1 to 6; R8 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, an alkyl moiety having 1 to 16 C atoms, preferably from 1 to 8 C atoms, or a phenyl moiety, a phenoxy moiety; - a thiuram residue of the formula (VII) (R9) 2N- (C = Z) - (VII) in which Z is sulfur or oxygen, R9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; - a dithioxantogenate moiety according to formula (VIII) R10-O-C (= S) - (VIII) in which R10 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 atoms of C, - a phosphonate residue according to formula (IX) (R11-O) (R11-O) P (Z) - (IX) in which Z is a sulfur or oxygen atom, R11 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, preferably 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 5 8 atoms of C. 6. The process according to claim 5, wherein the diene polymer is formed by polymerization of at least one conjugated diene monomer or at least one conjugated diene monomer with at least one vinyl aromatic comonomer. 7. The process according to claim 5 or claim 6, further comprising: react the diene polymer with a Mooney viscosity jump functionalization reagent. 8. The process according to claim 7, wherein the Mooney viscosity jump functionalization reagent is S2Cl2. 9. A modified polymer obtained according to the process of any of claims 5, 6, 7 or 8. 10. A rubber mixture, comprising: the modified polymer according to claim 1 or claim 2; and from 10 to 500 parts by weight of filler material, with respect to 100 parts by weight of the modified polymer. 11. A rubber mixture according to claim 10, further comprising: one or more of a rubber auxiliary and / or at least one additional rubber different from the modified polymer. 12. Vulcanizable composition comprising: the rubber mixture according to claim 10, and at least one crosslinking system comprising at least one crosslinker and optionally one or more crosslinking accelerators. 13. A process to produce vulcanized products, which includes: vulcanizing the vulcanizable composition according to claim 12. 14. The process according to claim 13, wherein said vulcanization step is carried out at a temperature in the range of 100 ° C to 200 ° C, preferably 120 ° C to 190 ° C. 15. Vulcanized obtained by the process according to claim 13 or 14. 16. The vulcanizates according to claim 15, said vulcanizates being formed in the form of shaped bodies, more preferably in the form of a transmission belt, roller covers, a seal, a cap, a plug, a hose , of floor coverings, of mats or sealing sheets, profiles or membranes. 17. The vulcanizates according to claim 15, said vulcanizates being formed in the form of tires, tire treads or layers thereof.